Post-treatment of electrospun nanofibers is a versatile and scalable approach for the fabrication of membranes with controlled pore size, porosity, and morphology. In this study, we demonstrate a novel solution-based approach for the fabrication of membrane distillation (MD) membranes with adjustable pore size and performance through non-solvent induced phase separation of a polymeric solution over an electrospun fiber mat. Poly(vinylidene fluoride-hexafluoropropylene) (PVDF-HFP) was dissolved in a blend of acetone and dimethylacetamide and used to produce a highly porous electrospun fiber mat with an average pore diameter of similar to 1.2 mu m. Surface coating of the PVDF-HFP nanofibers with polyvinylidene fluoride (PVDF) through phase separation enabled control of the membrane pore size by filling the empty domains between the fibers. The coated fiber mats were characterized for their surface hydrophobicity, porosity, and structure. The PVDF polymeric coating layer integrated within the electrospun mat decreased the average pore diameter to < 0.6 mu m without compromising the surface hydrophobicity. By controlling the depth of the PVDF coating layer within the substrate, we were able to fabricate robust membranes with near complete salt rejection (> 99.9%) and a water flux of 30 L m(-2) h(-1) in direct contact MD experiments with 40 degrees C temperature difference between the feed and permeate solutions. This coating procedure is compatible with current roll-to-roll membrane fabrication processes, making it a viable approach for large-scale fabrication of electrospun membranes with exceptional performance for MD applications.